Process for polyisocyanurate foams suitable for panels

ABSTRACT

Disclosed are novel polyol blends comprising from about 20 percent to about 85 percent by weight of said blend of an amine diol, or mixture of amine diols selected from the formula ##STR1## wherein R is an aliphatic radical having from 8 to 18 carbon atoms, inclusive, each R 1  is independently selected from the group consisting of hydrogen or methyl, x and y each independently have an average value from about 4 to about 15 inclusive; and from about 15 percent to about 80 percent by weight of a primary hydroxyl polyol characterized by a molecular weight of from about 60 to about 1000. 
     The polyol blends are miscible with fluorocarbon blowing agents and water and other adjuvants including trimerization catalysts. 
     The novel blends are particularly useful in an improved process for the preparation of polyisocyanurate foams. The foams are characterized by high reaction exotherms making such foams particularly suited to the preparation of polyisocyanurate foam laminates.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation-in-part of pending application Ser.No. 47,019 filed June 11, 1979, now abandoned.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to cellular polymers and intermediates thereforand is more particularly concerned with novel polyol blends and theiruse in a process for the preparation of cellular polyisocyanurates.

2. Description of the Prior Art

Cellular polyisocyanurate polymers are well known in the art for theiruse in various types of thermal insulating applications. They are alsowell known for their ability to withstand heat and flame; see U.S. Pat.Nos. 3,745,133, 3,986,991, and 4,003,859. Minor amounts of polyols aresometimes added to the foam forming ingredients to modify the foamproperties. When fluorocarbon blowing agents are employed the problem ofthe incompatibility that may arise between the polyol, particularlyprimary hydroxyl polyols, and fluorocarbon in resin premixes isgenerally solved by premixing most, if not all, the fluorocarbon withthe polyisocyanate; see the patents cited supra.

Polyisocyanurate foams find particular utility in the production oflaminated foam board stock material which can be prepared with a varietyof different facer materials. Problems which can arise in the productionof such laminate material include (1) lack of uniform foam corestrength; (2) poor adhesion between foam core and facer material; (3)maintaining good fire resistance in the form; and (4) keeping foamfriability at low levels. These problems have been overcome in the artby employing minor amounts of low equivalent weight polyols,particularly diols, in the formulation, combined with the heating of theformed laminate product in an oven at 160° to 190° F.; see U.S. Pat. No.3,903,346.

However, the low equivalent weight polyols employed, particularly thepreferred diols (see column 4, lines 59-61 of U.S. Pat. No. 3,903,346)having only primary hydroxyl groups, cannot be blended beforehand withthe fluorocarbon blowing agent in a "B" side component because of thelow solubility of the diol-fluorocarbon pair. This necessitates theblending of the fluorocarbon with the polyisocyanate in the "A" sidecomponent. Further, because of the fluorocarbon diol immiscibility, theabove patent teaches that a third component "C" is required whichcontains the catalyst constituent dissolved in a low molecular weightglycol; see column 2, lines 32-33 and the examples of U.S. Pat. No.3,903,346.

Furthermore, a laminate prepared in accordance with the patent notedabove must be heated in an oven to provide a product having a uniformfoam core strength.

Surprisingly, it has been found that high levels of fluorocarbon blowingagent are completely miscible with low molecular weight polyolscontaining primary hydroxyl groups when novel blends comprising acertain type of amine diol with the primary hydroxyl polyols areemployed. Additional ingredients which can be present in the miscibleblends are surfactants, catalysts, and the like.

Further, it has been found that the same type of miscible primaryhydroxyl containing blends as described above, except that waterreplaces the fluorocarbon component, can be obtained.

Furthermore, it has been discovered that the novel polyol blends abovecan be employed in minor amounts as a B type component to preparepolyisocyanate foams characterized by low friability, fine cellstructure, good dimensional stability, and low flame spread, via atwo-component, i.e., an A, and a B side, process. The fluorocarbon andwater components act as the blowing agents in their respective foamforming formulations.

Further, the amine diol referred to above can be employed as the solediol ingredient in combination with the fluorocarbon or water, catalyst,surfactant, and other adjuvants to provide polyisocyanurate foams inaccordance with the present invention.

Quite unexpectedly, the presence of the amine diol in the B side givesrise to excellent reactant compatibility between the polyisocyanate andthe other ingredients. This gives rise in turn to faster reactivitycompared to prior art foams and very good reaction exotherm. The highexotherm is of particular advantage when foam laminates are beingprepared because it results in excellent adhesion between foam and facermaterial thereby eliminating the need of heating the formed laminate inan oven.

SUMMARY OF THE INVENTION

This invention comprises polyol blends comprising from about 20 percentto about 85 percent by weight of said blend of an amine diol, or mixtureof amine diols selected from the formula ##STR2## wherein R is analiphatic radical having from 8 to 18 carbon atoms, inclusive, each R₁is independently selected from the group consisting of hydrogen ormethyl, x and y each independently have an average value from about 4 toabout 15 inclusive; and from about 15 percent to about 80 percent byweight of a primary hydroxyl polyol (II) charcterized by a molecularweight of from about 60 to about 1000.

This invention also comprises miscible blends arising from the abovepolyol blends in combination with a fluorocarbon or water blowing agent.

This invention also comprises miscible blends arising from the abovepolyol blends in combination with a fluorocarbon or water blowing agentand an isocyanate trimerization catalyst.

The invention also comprises a process for the preparation ofpolyisocyanurate cellular polymers which utilizes, as a blendedcomponent, the diol (I) above wherein the values of x and y can haveindependent average values of from about 1 to about 15 but preferablyfrom about 4 to about 15, with R and R₁ having the definitions set forthabove, in combination with a fluorocarbon or water blowing agent and atrimerization catalyst, and, preferably, the blended componentadditionally containing the polyol (II) in which case the diol (I) isdefined as above with the narrower range of x and y of about 4 to about15, in the reaction with an organic polyisocyanate.

The invention also comprises the cellular polymers produced inaccordance with the above process.

The invention also comprises a laminate panel having a polyisocyanuratefoam core made in accordance with the improved process in accordancewith the present invention.

The term "aliphatic radical" means alkyl and alkenyl having from 8 to 18carbon atoms inclusive. Representative of alkyl are octyl, decyl,dodecyl, tetradecyl, hexadecyl, octadecyl, and isomeric forms thereof.Representative of alkenyl ar octenyl, decenyl, dodecenyl, tetradecenyl,hexadecenyl, octadecenyl, and isomeric forms thereof.

The polyol blends in accordance with the present invention can be usedas the polyol ingredients in the preparation of polyurethane foams.Polyurethane foams are well known in the art for their use in a widevariety of applications including thermal and sound insulation for bothindustrial and residential buildings.

The polyol blends find particular utility, as set forth herein, as minorconstituents in the preparation of polyisocyanurate foams particularlythose polyisocyanurate foams prepared in foam laminate machinery and byspray foam equipment. Such foams are well known for their heat and fireresistance and are used in making laminate boards and foam bun stockwhich are both used in building construction for thermal and soundinsulation.

DETAILED DESCRIPTION OF THE INVENTION

The polyol blends in accordance with the present invention are preparedsimply by mixing together, in the proportions by weight set forth above,the amine diol (I) and primary hydroxyl polyol (II) defined above, inany suitable mixing vessel, holding tank, storage vessel, or the like.Preferably, the amine diol (I) is employed within a range of from about25 percent to about 60 percent by weight of the blend while the primaryhydroxyl polyol is employed within a range of from about 40 percent toabout 75 percent by weight.

A preferred amine diol has the formula corresponding to (I) wherein bothR₁ groups are hydrogen. A most preferrd amine diol has the formulacorresponding to (I) wherein both R₁ groups are hydrogen, and x and yeach independently have an average value from about 5 to about 10inclusive.

The amine diols (I) are prepared using standard reactions known to thoseskilled in the art and in some instances the amine diols arecommercially available. Typically, the amine diols (I) can be preparedby reacting the appropriate dialkanolamine with the appropriatealiphatic halide (R--X) compound, or mixture of different R--X compoundswhere all the aliphatic groups (R) fall within the definition above andX is halogen preferably chlorine or bromine. If the desired number ofalkyleneoxy groups are not already present in the dialkanolamine priorto reaction with the aliphatic halide they can be readily addedafterward by reacting the alkylated dialkanolamine with the appropriatenumber of moles of ethylene oxide or propylene oxide, or mixturesthereof, to provide the amine diols of formula (I).

Preferably, the amine diols (I) are prepared by reacting the appropriateprimary fatty amine R--NH₂ or mixture of fatty amines wherein all the Rgroups are defined as above, with from about 2 to about 30 moles,preferably from about 8 to about 30 moles, most preferably 10 to 20moles, of ethylene oxide or propylene oxide per molar proportion offatty amine; see Bulletin 1294, entitled Ethoxylated Fatty Amines,Ashland Chemical Company, Division of Ashland Oil Inc., Box 2219,Columbus, Ohio 43216 for a detailed teaching of the preparation of thesubject amine diols.

Illustrative of the starting fatty amines are octylamine, decylamine,dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, andisomeric forms thereof. Illustrative of the alkenylamines areoctenylamine, decenylamine, dodecenylamine, tetradecenylamine,hexadecenylamine, octadecenylamine, and isomeric forms thereof. Furtherillustrative of said fatty amines are mixtures of alkyl- andalkenylamines, for example, cocoamine which consists of the followingmixture in approximate percent proportions by weight: 2% decylamine, 53%dodecylamine, 24% tetradecylamine, 11% hexadecylamine, 5%octadecylamine, and 5% octadecenylamine; soya amine in the followingapproximate proportions: 11.5% hexadecylamine, 4% octadecylamine, 24.5%oleylamine, 53% linoleylamine, and 7% linolenylamine; and tallow aminein the following approximate proportions: 4% tetradecylamine, 29%hexadecylamine, 20% octadecylamine, and 47% octadecenylamine. Furtherillustrative of the starting fatty amines are the halogenated fattyamines, particularly the chlorinated and brominated fatty amines, which,illustratively, can be made by the chlorination or bromination ofcocoamine, soya amine, tallow amine, and the like.

A particularly preferred group of fatty amines consists of cocoaminemixture, soya amine mixture, and tallow amine mixture. A preferredmember of this group is cocoamine.

The primary hydroxyl polyol (II) can be any primary hydroxyl polyolhaving a molecular weight of from about 60 to about 1000, preferablyfrom about 60 to about 800, and most preferably from about 60 to about600. Included in the polyols (II) are diols, triols, and tetrols. Thepreferred polyols are diols.

Included in the class of primary hydroxyl containing polyols are thevarious primary hydroxyl containing diols, triols, and tetrols disclosedin U.S. Pat. No. 3,745,133 which meet the molecular weight limitationsset forth above and whose disclosure with respect to said polyols isincorporated by reference herein. The preferred classes are thepolyester polyols prepared from dibasic carboxylic acids and polyhydricalcohols including those based on chlorendic anhydride, alkylene diols,alkoxyalkylene diols, polyalkylene ester diols, polyoxyalkylene esterdiols, hydroxyalkylated aliphatic monoamines or diamines, the resolepolyols (see Prep. Methods of Polymer Chem. by W. R. Sorenson et al.,1961, page 293, Interscience Publishers, New York, N.Y.), andpolybutadiene resins having primary hydroxyl groups, (see Poly Bd LiquidResins, Product Bulletin BD-3, October 1974, Arco Chemical Company, Div.of Atlantic Richfield, New York, N.Y.).

The most preferred classes are the alkylene diols, lower alkoxyalkylenediols, polyalkylene ester diols, and polyoxyalkylene ester diols.

Illustrative, but not limiting, of the preferred classes of polyols inaccordance with the present invention are ethylene glycol,1,3-propanediol, 1,4-butanediol, glycerine, trimethylolpropane,pentaerythritol; diethylene glycol, the polyoxyethylene glycols preparedby the addition of ethylene oxide to water, ethylene glycol, ordiethylene glycol, etc., which provide triethylene glycol, tetraethyleneglycol, and higher glycols, or mixtures thereof such that the molecularweight falls within the range set forth above; ethoxylated glycerine,ethoxylated trimethylolpropane, ethoxylated pentaerythritol, and thelike; bis(β-hydroxyethyl)terephthalate, bis(β-hydroxyethyl)phthalate,and the like; polyethylene succinate, polyethylene glutarate,polyethylene adipate, polybutylene succinate, polybutylene glutarate,polybutylene adipate, copolyethylenebutylene succinate,copolyethylenebutylene glutarate, copolyethylenebutylene adipate, andthe like hydroxy terminated polyesters; polyoxydiethylene succinate,polyoxydiethylene glutarate, polyoxydiethylene adipate,polyoxydiethylene adipate glutarate and the like; diethanolamine,triethanolamine, N,N'-bis(β-hydroxyethyl)aniline, and the like.

The most preferred diols are diethylene glycol, and thepolyoxydiethylene adipate glutarate polyester diols having a molecularweight from about 400 to about 600.

Particularly preferred are blends of from about 30 percent to about 50percent by weight of diethylene glycol with from about 50 percent toabout 70 percent by weight of a polyoxydiethylene adipate glutaratepolyester diol having a molecular weight from about 400 to about 600.

In the preferred polyol blends in accordance with the present inventiona fluorocarbon or water blowing agent is also present in the blend withthe fluorocarbon being the preferred blowing agent.

When the blowing agent is a fluorocarbon the unexpected and advantageousfeatures of the polyol blends of (I) and (II) can be realized fully.Accordingly, there can be obtained miscible polyol blends comprising atleast about 25 percent by weight of a fluorocarbon blowing agent and thebalance being a polyol blend of (I) and (II) within the proportions setforth above.

Surprisingly, there are obtained miscible polyol blends comprising fromat least about 25 percent by weight to at least about 65 percent byweight of a fluorocarbon blowing agent and the corresponding 75 percentto about 35 percent by weight being the polyol blend of (I) and (II).The particular percentage of fluorocarbon to be dissolved in the blendwill govern the proportions of (I) and (II) to be employed in any giveninstance and these proportions, falling within the range set forthabove, can be easily determined by one skilled in the art by trial anderror methods.

Even more surprising is the fact that miscible polyol blends comprisinggreater than 65 percent by weight of fluorocarbon can be readilyobtained with the blends of (I) and (II) within the proportions setforth above in accordance with the present invention. Generallyspeaking, the lower the molecular weight of the primary hydroxyl polyol(II) the greater is the amount of fluorocarbon which can be dissolved inthe blend at a given proportion of polyol (II) as opposed to a blendwith a polyol (II) of higher molecular weight at the same proportion. Inthis connection, the alkylene diols, and lower alkoxyalkylene diolshaving molecular weights of less than 400 are preferred polyols offormula (II) with the latter lower alkoxyalkylene diols being mostpreferred.

The particular proportions of polyol (I) to polyol (II) to be employedin any particular polyol blend to obtain maximum miscibility withfluorocarbon can be determined by a process of trial and error.

When water is the blowing agent it is present in the proportions of fromabout 1 percent to about 6 percent, preferably from about 2 to about 5percent by weight with the balance of 94 percent to 99 percent andpreferably 95 to 98 percent comprising (I) and (II).

The fluorocarbon blowing agent can be any of the fluorocarbons known tothose skilled in the art and which can be used for blowing polymermixtures into cellular polymers. Generally speaking, such blowing agentsare halogenated aliphatic hydrocarbons which are also substituted bychlorine and/or bromine in addition to the fluorine content and are wellknown to those skilled in the art; see U.S. Pat. No. 3,745,133, column11, lines 25 to 38 which disclosure relating to fluorocarbon blowingagents is incorporated by reference herein.

In a preferred embodiment of a polyol blend in accordance with thepresent invention which finds particular utility in the preparation ofpolyisocyanurate foams, there is additionally present, in the blend ofblowing agent and components (I) and (II), an isocyanate trimerizationcatalyst. The isocyanate trimerization catalyst component will bediscussed in detail below. The isocyanate trimerization catalyst isadvantageously present in the proportions of from about 2 to about 20,preferably from about 2 to about 15 weight percent, with the balance ofabout 80 to about 98, preferably about 85 to 98 percent comprising theblend of (I), (II), and blowing agent set forth above.

Surprisingly, the blowing agent and the polyol blend which includes theprimary hydroxyl containing polyols are completely miscible in eachother with no separation occurring upon storage, which miscibility isdue to the presence of the amine diol (I). Aside from the advantagesarising from having a stable, miscible blend of primary hydroxyl polyoland fluorocarbon or water, the beneficial effects of having the aminediol present as a minor constituent when preparing polyisocyanuratefoams have been noted above.

Other optional additives can be added to the polyol blends withoutdetracting from the miscibility and stability of the blends. Suchadditives include other optional polyol components such as secondaryhydroxyl containing polyols, dispersing agents, cell stabilizers,surfactants, flame retardants, and the like which are commonly employedin the process of the invention.

In the preparation of polyisocyanurate foams in accordance with thepresent invention, the amine diol (I) described above can be employed asthe sole polyol component in admixture with a fluorocarbon or waterblowing agent and a trimerization catalyst to form a B side componentfor reaction with an A side comprised of an organic polyisocyanate. Inthis event the values of x and y in (I) can have the broader ranges asnoted above of from about 1 to about 15.

The percent by weight proportions of the blend ingredients are the sameas those set forth above for the proportions of catalyst to be blendedwith blowing agent and polyol component. That is to say the B blend iscomprised of from about 2 to about 20, preferably from about 2 to about15 percent by weight of a trimerization catalyst and from about 80 toabout 98, preferably about 85 to 98 percent by weight of amine diol (I)and blowing agent. In the event that a fluorocarbon blowing agent isemployed it is present in the proportions of about 20 to about 80,preferably from about 20 to about 50 percent by weight in respect of theamine diol (I), which, accordingly, is present from about 20 to about80, preferably from about 50 to about 80 percent by weight.

In the event that water is employed as the blowing agent it is presentin the proportions of from about 1 to about 6, preferably from about 2to about 5 percent by weight in respect of the amine diol (I), which,accordingly, is present from about 94 to about 99, preferably 95 to 98percent by weight.

The B side blend is advantageously employed in an amount falling withinthe range of from about 10 parts to about 120 parts, preferably fromabout 10 to about 80 parts, most preferably from about 20 parts to about60 parts by weight per equivalent of polyisocyanate; provided the totalhydroxyl equivalents present in said blend (B) are within a range offrom about 0.05 to about 0.5 equivalent, preferably about 0.08 to about0.4 equivalent, per equivalent of said polyisocyanate.

Preferably there is also present in the B side blend a minor amount ofthe primary hydroxyl polyol (II) described above. This combination inthe blend not only gives rise to the stabilized miscible blendsdiscussed above, but, additionally provides polyisocyanurate foamshaving the optimum advantageous properties discussed above, includingthe preparation of foam laminates which require no oven heating in orderto achieve maximum foam strength and adhesion to the laminate facers. Inthis event the values of x and y in (I) have the narrower ranges asnoted above of from about 4 to about 15.

The blend containing the amine diol (I) primary hydroxyl polyol (II),blowing agent, and trimerization catalyst is also employed in an amountfalling within the same range of parts per isocyanate equivalent setforth above for the B blend containing only the amine diol (I); and withthe same proviso set forth above for the range of total hydroxylequivalents per equivalent of isocyanate. The proportions of eachingredient in the blend in percent by weight of the blend are the sameproportions set forth in the description of the polyol blends. The aminediol (I), primary hydroxyl polyol (II) and blowing agent, all have thesame significance and scope set forth above.

The trimerization catalyst employed can be any catalyst known to thoseskilled in the art which will catalyze the trimerization of an organicisocyanate compound to form the isocyanurate moiety. Further, acombination of urethane forming catalyst and trimerization catalyst canbe employed if desired.

For typical isocyanate trimerization catalysts see The Journal ofCellular Plastics, November/December 1975, page 329; U.S. Pat. Nos.3,745,133, 3,896,052, 3,899,443, 3,903,018, 3,954,684, and 4,101,465,the disclosures of these references being hereby incorporated byreference herein.

Preferred as catalysts are the ones disclosed in U.S. Pat. Nos.3,896,052, and 4,101,465. The former reference discloses the catalystcombination of (a) an alkali metal salts of an N-substituted amide with(b) an alkali metal salt of an N-(2-hydroxyphenyl)methyl glycine andoptionally (c) a tertiary amine trimerization catalyst. The latterreference discloses the combination of the same (a) and (b) componentsabove with a hydroxyalkyltrialkylammonium carboxylate salt component.

The organic polyisocyanates which can be employed in the preparation ofthe polyisocyanurate foams in accordance with the present invention canbe any of the organic polyisocyanates conventionally employed in the artfor this purpose previously. Advantageously, and in order to obtainfoams having exceptionally high heat resistance and structural strength,the preferred polyisocyanates are the polymethylene polyphenylpolyisocyanates, particularly those set forth in U.S. Pat. No. 3,745,133whose disclosure with respect to said isocyanates is incorporated byreference herein. Also preferred are the polymethylene polyphenylpolyisocyanates treated with a minor amount of an epoxy compound toreduce acidic impurities in accordance with U.S. Pat. No. 3,793,362; andthe polymethylene polyphenyl polyisocyanates which contain high levelsof the 2,4'-isomer as typically disclosed in U.S. Pat. No. 3,362,979.

A most preferred organic polyisocyanate is a mixture containing fromabout 30 percent to about 85 percent by weight of methylenebis(phenylisocyanate) and the remainder of said mixture comprises polymethylenepolyphenyl polyisocyanates of functionality higher than 2.0.

In carrying out the preparation of polyisocyanurate foams in accordancewith the process of the invention, and, in particular, polyisocyanuratefoams for the preparation of foam laminates, the procedures andequipment conventional in the art are employed (see patents citedsupra); for a detailed teaching of the mode of preparation, and utilityof, polyisocyanurate foam laminates see U.S. Pat. No. 3,896,052 whosedisclosure relative thereto is incorporated by reference herein.

The following examples describe the manner and process of making andusing the invention and set forth the best mode contemplated by theinventors by carrying out the invention but are not to be construed aslimiting.

EXAMPLE 1

The following five polyisocyanurate foams (Foam A through E) wereprepared in accordance with the following procedure.

The foams were prepared as hand-mix samples by blending together the Aand the B side ingredients (in parts by weight) set forth in Table Ibelow, in 1 qt. cups. The polyisocyanate ingredient was the solecomponent of the A side while the B side ingredients which are listed inTable I were premixed and observed prior to being reacted with thepolyisocyanate. The blending operation was carried out by thoroughlymixing the A and B sides in the cup with a high speed drill press motorequipped with a stirrer blade. The mixture was rapidly poured into acardboard box and allowed to rise freely and cure at room temperature(circa 20° C.).

Foams B and E are in accordance with the present invention while A, C,and D are not because the amine diol component had values of x and ybelow that called for. The B sides in all of the formulations were clearwith no evidence of turbidity. However, in the case of A and C,secondary hydroxyl polyols were present which are known fluorocarbonsolubilizers while in C there was present additionally the phosphateplasticizer. Foam D also contained the plasticizing ingredient.

Maximum foam properties with respect to the combination of maximumreaction exotherm with rapid firm rate and low core and surfacefriability were observed with Foam E.

The surface blush in respect of a rising foam sample is the point whenthe shiny and moist unreacted surface of the rising foam becomes dulledor blushed and indicates that an efficient curing or reaction hasoccurred at the surface. All of the foam samples showed a good surfaceblush.

                  TABLE I                                                         ______________________________________                                        Foams       A       B       C      D     E                                    ______________________________________                                        Ingredients                                                                   (pts. by wt.)                                                                 A side:                                                                       Polyisocyanate I.sup.1                                                                    100     100     100    100   100                                  B side:                                                                       Diethylene glycol                                                                         5.7     5.4     6      6     8                                    Varonic® L-202.sup.2                                                                  5.7     --      6      6     --                                   Varonic® K-215.sup.3                                                                  --      23.5    --     --    8                                    Pluracol®                                                                 GP-730.sup.4                                                                              5.7     --      --     --    --                                   Pluracol®                                                                 PEP-650.sup.5                                                                             --      --      6      --    --                                   Tris(dichloropropyl-                                                          phosphate)  --      7.2     18     18    --                                   Propoxy-                                                                      lated polyol.sup.6                                                                        --      --      --     6     --                                   L-5420.sup.7                                                                              1.25    1.25    1.25   1.25  1.25                                 Fluoro-                                                                       carbon R-11B.sup.8                                                                        25      25      25     25    25                                   Catalyst I.sup.9                                                                          3       3       3      3     3                                    NCO/OH index                                                                              about   about   about  about about                                            4       4       4      4     4                                    Appearance of B                                                                           clear   clear   clear  clear clear                                component   and     and     and    and   and                                              not     not     not    not   not                                              turbid  turbid  turbid turbid                                                                              turbid                               Foam reaction                                                                 exotherm (°F.)                                                                     339     313     294    298   345                                  Firm rate   rapid   slow    medium rapid rapid                                Core friability                                                                           high    low     high   high  low                                  Surface friability                                                                        none    none    none   none  none                                 Surface blush                                                                             yes     yes     yes    yes   yes                                  ______________________________________                                         Footnotes to Table I                                                          .sup.1 Polyisocyanate I is a polymethylene polyphenyl polyisocyanate          containing about 45 percent by weight of methylenebis(phenyl isocyanate)      and the remainder of said mixture consisting of polymethylene polyphenyl      polyisocyanate having a functionality greater than 2; the isocyanate          equivalent = 133.                                                             .sup.2 Varonic® L202 is the soya amine adduct obtained by the reactio     of a 2 molar proportion of ethylene oxide with soya amine; amine              equivalent wt. about 360; hydroxyl equiv. wt. about 180; supplied by          Chemical Products Division, Ashland Chemical Company, Columbus, Ohio.         .sup.3 Varonic® K215 is the cocoamine adduct obtained by the reaction     of a 15 molar proportion of ethylene oxide with cocoamine; amine              equivalent wt. about 885; hydroxyl equiv. wt. about 442; supplied by          Chemical Products Division, Ashland Chemical Company, Columbus, Ohio.         .sup.4 Pluracol® GP730 is a propoxylated glycerine product; hydroxyl      equiv. wt. = 243, and is supplied by BASF Wyandotte Chemical Corp.,           Wyandotte, Mich.                                                              .sup.5 Pluracol® PEP650 is a propoxylated pentaerythritol product;        hydroxyl equiv. wt. = 148 and is supplied by BASF Wyandotte Chemical          Corp., Wyandotte, Mich.                                                       .sup.6 Propoxylated polyol is the product obtained from propoxylating a       mixture of sorbitol and toluene diamine to a hydroxyl number of 360,          viscosity of 2500 centistokes at 25° C., and specific gravity of       1.072.                                                                        .sup.7 L5420: A rigid foam silicone surfactant having a hydroxyl number o     about 119 supplied by Union Carbide Corp., Tarrytown, N.Y. 10591; see         Union Carbide Bulletin F43565, December 1971.                                 .sup.8 Fluorocarbon R11B is monofluorotrichloromethane blowing agent          stabilized with alloocimene and supplied by DuPont Chemical Corp.,            Wilmington, Del.                                                              .sup.9 Catalyst I comprises a combination in the following proportions of     (A.) 1 part of a solution comprised of (a) 45 percent by weight of            potassium Nphenyl-2-ethyl-hexamide, (b) 27 percent ethylene glycol, and       (c) 28 percent dimethylformamide; (B.) 3 parts of a solution comprised of     50 percent by weight of sodium N(2-hydroxy-5-nonylphenyl)methyl-N-methyl      glycinate in diethylene glycol; and (C.) 1 part of a solution comprised o     50 percent by weight of 2hydroxypropyltrimethylammonium formate and 50        percent dipropylene glycol; and (D.) 1 part of a polyethyleneglycol (MW =     200).                                                                    

EXAMPLE 2

The following foams were prepared in accordance with the procedure andapparatus described in Example 1 except as noted below. The foams ofthis example set forth a comparison of the prior art method (Foams F andH) versus the method in accordance with the present invention (Foams Gand I).

The ingredients of the A and B sides are set forth in Table II below.The F and G pair contained a different polyisocyanate from the H and Ipair. The A side of Foams F and H contained the fluorocarbon blowingagent in accordance with the prior art. When the same amount of thefluorocarbon was mixed into the B side to test miscibility, in bothcases, the fluorocarbon separated from the other ingredients, namely,diethylene glycol, surfactant, and catalyst.

In the case of Foams G and I which contained the ethoxylated cocoaminein the B side, the fluorocarbon and other ingredients were completelymiscible with the diethylene glycol component.

A comparison of the foam rise times between F and G, and H and I,clearly show a much faster rate for the foams in accordance with theinvention (G and I) over the respective pair in accordance with theprior art (F and H). The dramatic rate increase clearly indicates theincreased compatibility between the A and B sides which leads to betterreaction between the two hence the faster rise times over theformulations of the prior art. While the ethoxylated amine used in FoamsG and I is a tertiary amine, these types of high molecular weighttertiary amines are not strong bases and were used in G and I in verysmall amounts based on amine equivalents, i.e. 0.009 equivalents in eachcase. This low level of weak amine would not be enough to explain thedramatic rate increases of G and I over F and H respectively on thebasis of amine catalysis alone.

                  TABLE II                                                        ______________________________________                                        Foams            F       G       H     I                                      ______________________________________                                        Ingredients (pts. by wt.)                                                     A side:                                                                       Polyisocyanate I.sup.1                                                                         100     100     --    --                                     Polyisocyanate II.sup.2                                                                        --      --      105   105                                    Fluorocarbon R-11B                                                                             21.5    --      22.5  --                                     B side:                                                                       Diethylene glycol                                                                              8.3     8.0     8.3   8.0                                    Varonic® K-215                                                                             --      8.0     --    8.0                                    L-5420           1.25    1.25    1.25  1.25                                   Catalyst I       3.0     3.0     3.0   3.0                                    Fluorocarbon R-11B                                                                             --      23      --    24                                     NCO/OH index     4.6     4.2     4.6   4.2                                    Foam rise time (seconds)                                                      Cream            75      19      59    21                                     Gel              104     42      96    41                                     Tack free        116     49      106   47                                     Exotherm (°F.)                                                                          341     336     318   316                                    Core density, pcf                                                                              1.76    1.74    1.79  1.75                                   Dry heat age 300° F./24 hrs.                                           % Δ volume +4.6    +4.1    +2.9  +2.4                                   Core friability, %.sup.3                                                                       31      30      22    19                                     Surface friability                                                                             none    none    none  none                                   Surface blush    yes     yes     yes   yes                                    ______________________________________                                         Footnotes to Table II                                                         .sup.1 See Footnote 1, Table 1.                                               .sup.2 Polyisocyanate II is a polymethylene polyphenylpolyisocyanate          containing about 35 percent by weight of methylenebis(phenyl isocyanate)      and the remainder of said mixture consisting of polymethylene polyphenyl      polyisocyanate having a functionality greater than 2; the isocyanate          equivalent = 140.                                                             .sup.3 The friability is the percent sample weight loss over a 10 minute      period and determined in accordance with ASTM Test method C421.          

EXAMPLE 3

The following two polyisocyanurate foams J and K in accordance with thepresent invention were prepared in accordance with the procedure andapparatus described in Example 1 and using the ingredients in theproportions by weight set forth in Table III below. The B componentswere clear in both cases.

Both foams were very fine celled in structure with no surface friabilityand a good surface blush was observed. The foam exotherms were good andthe rapid rise profiles indicated the fast reactivity for both foams.

It is noteworthy that the catalyst mixture employed in both J and Kcontained a very minor amount of the Varonic® K-215 amine diol whichacted as a compatibilizing agent for the various other catalystcomponents. In the absence of the Varonic® K-215 the other catalystcomponents are not completely miscible.

                  TABLE III                                                       ______________________________________                                        Foam               J          K                                               ______________________________________                                        Ingredients (pts. by wt.)                                                     A side:                                                                       Polyisocyanate III.sup.1                                                                         135        135                                             B side:                                                                       Varonic® K-205.sup.2                                                                         37         --                                              Varonic® K-215 --         75                                              DC-193.sup.3       1.5        1.5                                             Fluorocarbon R-11B 22         27                                              Catalyst II.sup.4  3          3                                               NCO/OH index       4.5        4.5                                             B mix appearance   clear      clear                                           Foam rise time (seconds)                                                      Cream              5          6                                               Gel                20         20                                              Tack free          30         40                                              Rise               --         --                                              Exotherm (°F.)                                                                            328        305                                             Surface friability none       none                                            Surface blush      yes        yes                                             Core friability    low        low                                             Appearance         very fine  very fine                                                          cell       cell                                            ______________________________________                                         Footnotes to Table III                                                        .sup.1 Polyisocyanate III is a polymethylene polyphenyl polyisocyanate        containing about 45 percent by weight of methylenebis (phenyl isocyanate)     and the remainder of said mixture consisting of polymethylene polyphenyl      polyisocyanates having a functionality greater than 2, the isocyanate         equivalent = 135.                                                             .sup.2 Varonic® L205 is the cocoamine adduct obtained by the reaction     of a 5 molar proportion of ethylene oxide with cocoamine; amine equivalen     wt. = about 445; hydroxyl equiv. wt. about 222; supplied by Chemical          Products Division, Ashland Chemical Company, Columbus, Ohio.                  .sup.3 DC193 is a silicone surfactant supplied by Dow Corning, Midland,       Mich.; see Bulletin 05146, February 1966.                                     .sup.4 Catalyst II comprises a combination in the following proportions       of: (A.) 1 part of a solution comprised of 50 percent by weight of sodium     N(2-hydroxy-5-nonyl phenyl)methylN-methyl glycinate in diethylene glycol;     (B.) 0.50 part of potassium acetate; (C.) 0.30 part of water; and (D.)        0.50 part of Varonic® K215 which is described in Footnote 3 of Table      above. It should be noted that this catalyst blend is completely clear an     miscible. Preparation of the same catalyst blend but without the K215         component yields a turbid and cloudy mixture.                            

EXAMPLE 4

The following two water blown polyisocyanurate foams L and M wereprepared in accordance with the present invention using the procedureand apparatus described in Example 1 and using the ingredients in theproportions by weight set forth in Table IV below. The B side in bothcases formed a clear miscible blend.

The foam rise characteristics were found to be very rapid with a quicktack free time in spite of the foams being water blown. High foamexotherms were also observed attesting to the excellent conversions. Theresulting foam physical properties were good.

                  TABLE IV                                                        ______________________________________                                        Foams                 L         M                                             ______________________________________                                        Ingredients (pts. by wt.)                                                     A side:                                                                       Polyisocyanate III    135       135                                           B side:                                                                       Polyol blend I.sup.1  23        30                                            L-5420                2         2                                             H.sub.2 O             1         1                                             Catalyst II           3         3                                             NCO/OH index (including H.sub.2 O)                                                                  3         2.5                                           B mix appearance      clear     clear                                         Foam rise time (seconds)                                                      Cream                 15        13                                            Gel                   31        26                                            Rise                  48        48                                            Tack free             35        30                                            Exotherm (°F.) 376       383                                           Density (pcf)         2.65      2.81                                          K-factor.sup.2 in                                                             BTU (ft..sup.2) (hr.) °F./in.:                                         in ∥ dir.    0.190     0.201                                         in ⊥ dir.        0.189     0.193                                         Compressive str. (psi)                                                        ∥ to rise    39.5      42                                            ⊥ to rise        30.0      20                                            % Δ Volume at 70° C., 100%                                       relative humidity after                                                       24 hrs.               -7.7      -4.7                                          300° F. Dry Age Δ Volume (%)                                     after 24 hrs.         -2.9      +3.0                                          ______________________________________                                         Footnotes to Table IV                                                         .sup.1 Polyol blend I comprises a blend in the following proportions of       (A.) 40.8 pts. of a polyoxydiethylene adipate glutarate polyester diol of     M.W. = 500; (B.) 28.6 pts. of diethylene glycol; and (C.) 30.6 pts. of        Varonic® K215.                                                            .sup.2 KFactor is a measure of thermal conductivity of materials by           determining heat flow in accordance with ASTM Test method C518.          

EXAMPLE 5

This example sets forth a hand-mix polyisocyanurate foam N prepared inaccordance with the present invention using the procedure and apparatusdescribed in Example 1 and the ingredients set forth in Table V below.

The B side of sample N contained a mixture of primary hydroxyl triol anddiethylene glycol with a 41% by weight proportion of fluorocarbon yetthe blend stayed clear with no turbidity.

The foam had fast rise times with a good exotherm and good friabilitycharacteristics.

                  TABLE V                                                         ______________________________________                                        Foam                   N                                                      ______________________________________                                        Ingredients (pts. by wt.)                                                     A side:                                                                       Polyisocyanate III     135                                                    B side:                                                                       TPEG-990.sup.1         8.5                                                    Diethylene glycol      6.5                                                    Varonic® K-215     10                                                     DC-193                 1.25                                                   Catalyst II            3.0                                                    Fluorocarbon R-11B     20                                                     B mix appearance       clear                                                                         no turbidity                                           % R-11B in B mix       41%                                                    Foam rise time (seconds)                                                      Cream                  13                                                     Gel                    30                                                     Tack free              35                                                     Exotherm (°F.)  349                                                    Surface friability     none                                                   Surface blush          yes                                                    Core friability        low                                                    ______________________________________                                         Footnote to Table V                                                           .sup.1 TPEG990 is a primary hydroxyl containing trifunctional polyethylen     glycol having an OH E.W. = 333; and is supplied by Union Carbide Corp.,       New York, N.Y.                                                           

EXAMPLE 6

The following high temperature and flame resistant polyisocyanurate foamlaminates were prepared in accordance with the present invention usingthe foam O which was prepared from the ingredients set forth in Table VIbelow.

A Viking laminating machine was used with "A" and "B" componenttemperatures of 73° F. and 70° F. respectively. Throughput was 15lbs./min. through a low pressure impingement mixing head. A pour laydown technique was used instead of a nip roll. The conveyor speed was 10ft./min. and the curing oven temperature was at ambient (70° to 90° F.).

Two inch thick laminate was prepared with 0.0015" aluminum foil facersand also prepared with asphalt facers. The foam properties reported inTable VI below are for the foam core material after the facers had beenremoved. Therefore, the facer material itself has no affect on thisdata. The adhesion between facer material and foam was excellent.

The component B, although containing the primary hydroxyl polyester anddiethylene glycol and a 43% by weight content of freon (R-11B) was clearwith no turbidity.

The laminates were prepared without the necessity of oven curing at ahigh temperature because of the rapid reactivity of the formulation. Therapid reactivity also was reflected in the rapid rise profile and thefact that foam friability was found to be very low in spite of the lackof a high temperature cure step. Good facer adhesion, as noted above,was also observed.

The overall foam physical properties were found to be good including thevery low friability, good fire resistance, K factor, and humid age data.

                  TABLE VI                                                        ______________________________________                                        Foam                    O                                                     ______________________________________                                        Ingredients (pts. by wt.)                                                     A side:                                                                       Polyisocyanate I        133                                                   B side:                                                                       Polyester diol.sup.1    9                                                     Diethylene glycol       6.3                                                   Varonic® K-215      6.7                                                   DC-193                  1.25                                                  Catalyst II             3.0                                                   Fluorocarbon R-11B      20.0                                                  B mix appearance        clear                                                                         no turbidity                                          % R-11B in B mix        43%                                                   NCO/OH index            4.9                                                   Foam rise time (seconds)                                                      Cream                   19                                                    Gel                     40                                                    Tack free               47                                                    Surface friability      none                                                  Surface blush           yes                                                   Core friability         low (6%)                                              Overall density (pcf)   2.0                                                   Core density            1.8                                                   Compressive str.(psi)                                                         ∥ to rise      31                                                    Compressive str. (psi)                                                        ⊥ to rise          21                                                    Closed cells.sup.2      94%                                                   K Factor in                                                                   BTU (ft..sup.2) (hr.) °F./in.                                                                  0.14                                                  Humid age (158° F., 95% R.H.)                                          Δ Vol., after 1 day                                                                             +6%                                                   7 days                  +6.5%                                                 28 days                 +7.0%                                                 ASTM E-84 Test on 2" thick                                                    samples:                                                                      Flame spread rating     38                                                    Smoke                   187                                                   ______________________________________                                         Footnotes to Table VI                                                         .sup.1 Polyester diol is the same diol described in Footnote 1 of Table I     under A.                                                                      .sup.2 Closed cells are determined by the air pycnometer test in              accordance with ASTM Test method D2856.                                  

EXAMPLE 7

A series of blends of fluorocarbon R-11B (monofluorotrichloromethane)with two typical primary hydroxyl polyols of the present invention wereprepared. The proportions by weight employed, including the amount ofamine diol when present, varied according to the values set forth inTable VII below. The blends were observed for their miscibility andclearness or their turbidity and separation of the fluorocarbon fromsolution.

Blends A through D contained diethylene glycol with fluorocarbon and inthe absence of amine diol, i.e., 100% diethylene glycol, the maximumfluorocarbon solubility was 15% by weight. The addition of 10 percent bywt. amine diol was not sufficient to impart fluorocarbon solubility atthe 25% by wt. level whereas a 20 percent amine diol content (blend D)did result in a clear miscible solution at 25 percent fluorocarbon.

Blends E through J contained a polyester diol defined above wherein thepure polyester diol was capable of dissolving 20 percent by weightfluorocarbon but not 25 percent. The break for 25 percent fluorocarbonsolubility started at about 10 parts by weight of the amine diol (blendG) while at the 20 percent level of amine diol the fluorocarbon couldreach up to 31 percent by wt.

Blends K through M were observed to have maximum fluorocarbon levels ofgreater than 90 percent and up to 67.5 percent for diethylene glycol andthe polyester diol respectively when a maximum of 85 percent by weightof amine diol was employed.

Blends N through Q were observed to have maximum fluorocarbonsolubilities of 60 percent and 50 percent respectively for diethyleneglycol and polyester diol when the primary alcohol-amine diol blendswere 50/50 percent by weight.

                                      TABLE VII                                   __________________________________________________________________________    Blend        A    B    C    D    E    F    G    H    I                        __________________________________________________________________________    Ingredients (pts. by wt.)                                                     Diethylene glycol                                                                          100  100  90   80   --   --   --   --   --                       Polyester diol.sup.1                                                                       --   --   --   --   100  100  90   80   80                       K-215.sup.2  --   --   10   20   --   --   10   20   20                       Fluorocarbon R-11B                                                                         17.6 25   33.3 33.3 25   33.3 33.3 40   45                       % by wt. primary alcohol                                                                   100  100  90   80   100  100  90   80   80                       % by wt. amine diol                                                                        0    0    10   20   0    0    10   20   20                       % by wt. fluorocarbon                                                                      15   20   25   25   20   25   25   28.5 31                       Blend appearance                                                                           clear                                                                              turbid                                                                             turbid                                                                             clear                                                                              clear                                                                              turbid                                                                             clear                                                                              clear                                                                              clear                                 miscible                                                                           separates                                                                          separates                                                                          miscible                                                                           miscible                                                                           separates                                                                          miscible                                                                           miscible                                                                           miscible                 __________________________________________________________________________    Blend              J   K    L    M    N    O    P    Q                        __________________________________________________________________________    Ingredients (pts. by wt.)                                                     Diethylene glycol  --  15   --   --   50   50   --   --                       Polyester diol.sup.1                                                                             80  --   15   15   --   --   50   50                       K-215.sup.2        20  85   85   85   50   50   50   50                       Fluorocarbon R-11B 50  900  207.7                                                                              233.3                                                                              150  175  100  120                      % by wt. primary alcohol                                                                         80  15   15   15   50   50   50   50                       % by wt. amine diol                                                                              20  85   85   85   50   50   50   50                       % by wt. fluorocarbon                                                                            33.3                                                                              90   67.5 70   60   63.6 50   55                       Blend appearance   cloudy                                                                            clear                                                                              clear                                                                              turbid                                                                             clear                                                                              turbid                                                                             clear                                                                              turbid                                          miscible                                                                           miscible                                                                           separates                                                                          miscible                                                                           separates                                                                          miscible                                                                           separates                __________________________________________________________________________     Footnotes to Table VII                                                        .sup.1 The same polyester diol described in Footnote 1 of Table IV under      A.                                                                            .sup.2 K215 is the amine diol defined in Footnote 3 of Table I.          

We claim:
 1. In a process for the preparation of a cellular polymer inwhich the major recurring polymer unit is an isocyanurate moiety saidprocess comprising the trimerization of an organic polyisocyanate in thepresence of a minor amount of a polyol, a blowing agent, and atrimerization catalyst, the improvement which comprises preparing saidcellular polymer by bringing together:A. an organic polyisocyanate; andB. from about 10 to about 120 parts by weight per equivalent of saidpolyisocyanate of a blend comprising:(a) about 2 to about 20 percent byweight of a polyisocyanate trimerization catalyst, and (b) about 80 toabout 98 percent by weight of a mixture comprising:1. about 20 to about80 percent by weight of a fluorocarbon blowing agent, and
 2. about 20 toabout 80 percent by weight of a polyol component comprising an aminediol or mixture of amine diols selected from the formula ##STR3##wherein R is an aliphatic radical having from 8 to 18 carbon atoms,inclusive, each R₁ is independently selected from the group consistingof hydrogen or methyl, x and y each independently have an average valuefrom about 1 to about 15 inclusive; andprovided the total hydroxylequivalents present in said blend (B) are within a range of from about0.05 to about 0.5 equivalent per equivalent of said polyisocyanate. 2.In a process for the preparation of a cellular polymer in which themajor recurring polymer unit is an isocyanurate moiety said processcomprising the trimerization of an organic polyisocyanate in thepresence of a minor amount of a polyol, a blowing agent, and atrimerization catalyst, the improvement which comprises preparing saidcellular polymer by bringing together:A. an organic polyisocyanate; andB. from about 10 to about 120 parts by weight per equivalent of saidpolyisocyanate of a blend comprising:(a) about 2 to about 20 percent byweight of a polyisocyanate trimerization catalyst, and (b) about 80 toabout 98 percent by weight of a mixture comprising:1. about 1 to about 6percent by weight of water, and
 2. about 94 to about 99 percent byweight of a polyol component comprising an amine diol or mixture ofamine diols selected from the formula ##STR4## wherein R is an aliphaticradical having from 8 to 18 carbon atoms, inclusive, each R₁ isindependently selected from the group consisting of hydrogen or methyl,x and y each independently have an average value from about 1 to about15 inclusive; andprovided the total hydroxyl equivalents present in saidblend (B) are within a range of from about 0.05 to about 0.5 equivalentper equivalent of said polyisocyanate.
 3. In a process for thepreparation of a cellular polymer in which the major recurring polymerunit is an isocyanurate moiety said process comprising the trimerizationof an organic polyisocyanate in the presence of a minor amount of apolyol, a blowing agent, and a trimerization catalyst, the improvementwhich comprises preparing said cellular polymer by bringing together:A.an organic polyisocyanate; and B. from about 10 to about 120 parts byweight per equivalent of said polyisocyanate of a miscible blendcomprising:(a) about 2 to about 20 percent by weight of a polyisocyanatetrimerization catalyst, and (b) about 80 to about 98 percent by weightof a mixture comprising:1. at least about 25 percent by weight of afluorocarbon blowing agent, and
 2. the balance being a polyol mixturecomprising:(i) about 20 to about 85 percent by weight of an amine diol,or mixture of amine diols selected from the formula ##STR5## wherein Ris an aliphatic radical having from 8 to 18 carbon atoms, inclusive, andx and y each independently have an average value from about 4 to about15 inclusive; and (ii) about 15 to about 80 percent by weight of aprimary hydroxyl polyol characterized by a molecular weight of fromabout 60 to about 1000; andprovided the total hydroxyl equivalentspresent in said blend (B) are within a range of from about 0.05 to about0.5 equivalent per equivalent of said polyisocyanate.
 4. A processaccording to claim 3 wherein said polyisocyanate is a polymethylenepolyphenyl polyisocyanate.
 5. A process according to claim 3 whereinsaid polyol (ii) is a primary hydroxyl diol.
 6. A process for thepreparation of a cellular polymer in which the major recurring polymerunit is an isocyanurate moiety said process comprising bringingtogether:A. a polymethylene polyphenyl polyisocyanate; and B. from about10 to about 120 parts by weight per equivalent of said polyisocyanate ofa miscible blend comprising:(a) about 2 to about 20 percent by weight ofa polyisocyanate trimerization catalyst, and (b) about 80 to about 98percent by weight of a mixture comprising:1. at least about 25 percentby weight of a fluorocarbon blowing agent, and
 2. the balance being apolyol mixture comprising:(i) about 20 to about 85 percent by weight ofan ethoxylated cocoamine diol mixture obtained from the reaction ofabout 15 moles of ethylene oxide with cocoamine, and (ii) about 15 toabout 80 percent by weight of a primary hydroxyl diol having a molecularweight of from about 60 to about 800; andprovided the total hydroxylequivalents present in said blend (B) are within a range of from about0.05 to about 0.5 equivalent per equivalent of said polyisocyanate.
 7. Aprocess according to claim 6 wherein the primary hydroxyl diol (ii) isdiethylene glycol.
 8. A process according to claim 6 wherein the primaryhydroxyl diol (ii) is a polyoxydiethylene adipate glutarate polyesterdiol having a molecular weight from about 400 to about
 600. 9. A processaccording to claim 6 wherein the primary hydroxyl diol (ii) comprises amixture of from about 30 percent to about 50 percent by weight ofdiethylene glycol and from about 50 percent to about 70 percent byweight of a polyoxydiethylene adipate glutarate polyester diol having amolecular weight from about 400 to about
 600. 10. A laminate panelcomprising a foam core made in accordance with the process set forth inclaim 3 and having the opposing faces of said core bonded to a facingmaterial.